Zirconium metal organic frameworks-based DGT technique for in situ measurement of dissolved reactive phosphorus in waters.

In an effort to provide early warnings for the occurrence of eutrophication, it is highly desirable to develop an accurate and efficient technique to ensure continuous monitoring of dissolved reactive phosphorus (DRP) in the aquatic environment from the viewpoint of environmental management. Herein, a new diffusive gradient in thin film (DGT) technique was developed and evaluated for in situ measurement of DRP in waters, in which Zr-based metal organic frameworks (MOFs, UiO-66) were utilized as aqueous binding agent (abbreviated as UiO-66 DGT). As expected, the UiO-66 DGT demonstrated high uptake capacity towards phosphorus (20.8 µg P cm-2). Meanwhile, an excellent linearity between the accumulated DRP mass and deployment time over 5 d (R2 = 0.996) was obtained regardless of high or low phosphate solution. In addition, effective diffusion coefficients (D) of DRP increased exponentially with increasing ionic strengths (R2 = 0.99). Based on the rectified D, the performance of the UiO-66 DGT was independent of solution pH (6.5-8.5) and ionic strengths (ranging from 0.01 to 100 mmol L-1). Furthermore, field deployments of the UiO-66 DGT were undertaken in a natural eutrophic lake (Lake Chaohu, China). It was noteworthy that DRP could be continually accumulated by the UiO-66 DGT for more than 14 d and good agreements were obtained between the concentrations measured by DGT (CDGT) and those by ex situ chemical extraction method in solution (Csol), as reflected by CDGT/Csol of 0.9-1.1. In situ determination of DRP speciation was also carried out at different sites across Lake Chaohu. Overall, this study contributed to a better constructing of liquid binding phase DGT for the measurement of DRP in waters, facilitating the widespread application of the UiO-66 DGT as a routine monitoring technique and for large-scale environmental analysis.

Electrokinetic delivery of persulfate to remediate PCBs polluted soils: effect of injection spot.

Persulfate-based in situ chemical oxidation (ISCO) is a promising technique for the remediation of organic compounds contaminated soils. Electrokinetics (EK) provides an alternative method to deliver oxidants into the target zones especially in low permeable-soil. In this study, the flexibility of delivering persulfate by EK to remediate polychlorinated biphenyls (PCBs) polluted soil was investigated. 20% (w/w) of persulfate was injected at the anode, cathode and both electrodes to examine its transport behaviors under electrical field, and the effect of field inversion process was also evaluated. The results showed that high dosage of persulfate could be delivered into S4 section (near cathode) by electroosmosis when persulfate was injected from anode, 30.8% of PCBs was removed from the soil, and the formed hydroxyl precipitation near the cathode during EK process impeded the transportation of persulfate. In contrast, only 18.9% of PCBs was removed with the injection of persulfate from cathode, although the breakthrough of persulfate into the anode reservoir was observed. These results indicated that the electroosmotic flow is more effective for the transportation of persulfate into soil. The addition of persulfate from both electrodes did not significantly facilitate the PCBs oxidation as well as the treatment of electrical field reversion, the reinforced negative depolarization function occurring in the cathode at high current consumed most of the oxidant. Furthermore, it was found that strong acid condition near the anode favored the oxidation of PCBs by persulfate and the degradation of PCBs was in consistent with the oxidation of Soil TOC in EK/persulfate system.